Aziridinium nitrophenolates



United States Patent 3,335,132 AZINIUM NITROPHENOLATES Stephen J. Kuhn, Sarnia, Ontario, Canada, assignoito The Dow Chemical Company, Midland, Mich., a cor- 3,335,132 Patented Aug. 8, 1967 ture below that at which the salt decomposes or the aziridine polymerizes. Suitable such temperatures are -20 to 30 C., though high temperatures, even up to 100 can be used with the more stable salts.

omfio of Delaware 5 Suitable solvents include the aliphatic and aromatic p N 0 Filed Oct. 7 1964 Sen No' 402 331 hydrocarbons and ethers, such as benzene, toluene, Xylene, 6 Claims. 260L239) hexane, octane, petroleum ether, diethyl ether, dibutyl ether, tetrahydrofuran and the like.

This invention relates to new compounds which are Suitable aziridines are those having no substituent in the aziridine salts of certain nitrophenols. They may be 10 the 1-position and only inert substituents in the 2- and/ or represented by the formula 3-position, thus including aziridine itself as well as 2- O alkylaziridines, such as Z-methylaziridine, Z-ethylaziridine I and the isomeric 2-butylaziridines, 2-phenylaziridine, 2-

+/ methyl-3-phenylaziridine, 2,3-dimethylaziridine and 2- (Noz) (MW methyl-3-butylaziridine. Preferably, any substituents contain no more than 6 carbon atoms.

Suitable phenols are those having at least one nitro wherein x is an integer l-2, R is H or an inert radical, group attached to the aromatic Ting bearing a Phellolic such as alkyl or phenyl and each A is H or an inert Y Y P- other Substituents y also be Present radical, Such as alkyl or halogen on the ring so long as they are inert toward aziridine According to the known art, phenols readily react i under the conditions of the process. Examples of suitable aziridines to open the aziridine ring. Phenol itself is thus P lllelude q pp the Various etherified to produce zhmihoalkyl phehyl ethel-s in d isomeric nitrocresols; the nitrohalophenols, such as the tion to polymers of the aziridine. 0-, mand p-Nitronitrochlorophenols, the nitrobromophenols, the nitrophenols do not form ethers but catalyze ring-opening and ehlofe'eresels and the llltfobromoeresolsg dini'lfopolymerization of the aziridine [L. B. Clapp, I. Am. P suflh and gfip the h Soc 73 2534 1951 Aziridihes have been corresponding dinitrocresols; the dinitrohalophenols, such acted with picric acid to produce crystalline salts, the as ehlOrO- and 2jbr0m0-3,5-dinitrephenol, P P picryl group being said to be analogous to an acyl group. and p f m These salts are easily hydrolyzed, alcoholyzed or rear- P l and P P 111 general ranged to N-(Z-hydroxyalkyl)picramides (L. B. Clapp y flltfopllenol havlffg one Or tWO 1mm groups and 110 et h Am. Chem SOC 77 51 1955 It thus other substituent reactive with aziridine. Non-reactive subpears from the prior art that a phenol and an aziridine Stltuents Include elkyl ee aryl, Particularly P y can reactin any f three Ways; groups, preferably containing no more than 6 carbon 1 The h 1 can directly attack h -i i Openatoms each and halogens, especially chlorine and bromine. ing the ring and f i a ghminoalkyl ether f the The practice of the invention is illustrated by the folphenol (e.g., phenol itself). IOWlng examples- (2) Polymerization of the aziridine may be catalyzed, General procedure even though no phenyl ether is formed (e.g. mononitroand monohalophenols as taught by Clapp). 4.0 A solution of 0.2 mole of the nitrophenol in 500 ml.

(3) An aziridinium phenolate may be formed as a stable of anther was ,Stlrred and mamtameq a f t emperature salt (eg picric acid) (25 C.) while 0.2 mole of the aziridine, optionally dis- Prior to the Present invention, no phenol other than solved 1n ether, was slowly added. The crystalline salt Picric acid, which is a most unusual and atypical phenol, precipitated as formed and was separated by filtration. A was known to form a stable salt with an aziridine. By Small amount of Product could be recovered by P stable salt is meant one capable of isolation and existnon of e filtrate- The Products were hlghly Colored ence at ordinary temperatures crystals which were stable at room temperature, and in According to the present invention, stable, crystalline most cases, P to their melting p The free aZiridine aziridinium in-o he olat r d b t ti an could be recovered from the salts by treatment with alkali. aziridine having an unsubstituted ring nitrogen atom with Table 1 lists some yp Salts prepared by the above a nitrophenol in an inert, anhydrous solvent at a temperaprocedure.

TABLE I OH; At-ONHz CBS-R N Percent Example Ar R M.P., Yield N 0. 0. Percent Found Calcd 1 2,4-dinitropheny1 111-113 18.56 18.50 2 .do 97-99 96 17. 50 17. 42 3 2methyl-4,fi-dinitrophenyL. 98-99 95 17.70 17.65 4 do 0H3 93-94 95 16. 39 16. 47 5 2, (rdichloro-4-nitr0phenyl H -112 94 11.15 11.20 a dn CH3 96. 9s 95 10. 61 10. 56 7 2-nitro-3,4,fi-ti'ichlorophenyl H 106.107 98 9.80 9.80 8 do CH 99.101 97 9. 43 9. 49 9 2-nitr0phenyl H 108-110 89 15.34 15.38

The compounds of the invention are useful as stable, non-volatile sources of the aziridine component. They are also useful as pesticides. As herbicides, the compounds of Examples -1, 3, 5 and 7 killed substantially, 100 percent of crabgrass and radish while aziridinium picrate at the same concentrations (0.4 percent and 0.005 percent on radish and crabgrass, respectively) showed substantially zero kill. Similarly, in the control of water weeds, the compound of Example 7, at a concentration of 10 parts per million, showed 100 percent kill of Elodea and Cabomba and 90 percent kill of milfoil while aziridinium picrate showed zero kill on all three weeds at the same concentration. As insecticides, when applied to two-spotted spider mites in a concentration of 0.05 percent, the compounds of Examples 1, 2, 4 and 7 efiected substantially 100 percent kill while aziridinium picrate in the same testshowed zero kilLAs fish poisons, the compounds of Examples 3 and 4 killed 100 percent of goldfish at a concentration of 2 parts per million while aziridinium picrate in the same test killed Opercent;

I claim: 1. An aziridinium nitrophenolate having the formula CH-R o- Knrf I OH-R wherein x is an integer 1-2, eachR is an inert radical selected from the group consisting of H, alkyl and aryl radicals containing up to 6 carbon atoms and each A' is a radical selected from the group consisting of H, halogen, aryl and alkyl radicals containing up to 6 carbon atoms.

2. An aziridinium nitrophenolate having the formula CH (GnH2n-H) wherein x is an integer 1-2, y is an integer 0-3 and n and z are integers 0-1.

3. The process for making a crystalline aziridinium nitrophenolate comprising reacting by contacting at a temperature below the decomposition point of the nitrophenolate and in an inert anhydrous solvent, a nitrophenol of the formula 2) is )5x wherein x is an integer 1-2 and A isH, halogen, aryl or alkyl and contains not more than 6 carbon. atoms, with an aziridine having the formula CHR CHR

wherein each R is H or an inert alkyl or. aryl radical and contains not more than 6 carbon atoms.

4. The process of claim '3 wherein the nitrophenol has the formula UNITED STATES PATENTS 8/1940 "Mills 2 -4 22 10/1946 Fletcher et -al. 260-622 OTHER REFERENCES Braude et al.: Determination of Organic Structures by Physical Methods (New York, 1955), pages 589-596.

Frear, Chemistry of the Pesticides (New York, 1955), pages 384-385.

Schatz et -a1.: J. Am. Chem.,So'c., vol. 77, pages 5113- 5118 (1955).

ALEX MAZEL, Primary Examiner.

ALTON D. ROLLINS, Examiner. 

1. AN AZIRIDINIUM NITROPHENOLATE HAVING THE FORMULA
 3. THE PROCESS FOR MAKING A CRYSTALLINE AZIRIDINIUM NITROPHENOLATE COMPRISING REACTING BY CONTACTING AT A TEMPERATURE BELOW THE DECOMPOSITION POINT OF THE NITROPHENOLATE AND IN AN INERT ANHYDROUS SOLVENT, A NITROPHENOL OF THE FORMULA 